CN100383053C - Method for recovering and making antimony oxide from antimony pentachloride solution - Google Patents
Method for recovering and making antimony oxide from antimony pentachloride solution Download PDFInfo
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- CN100383053C CN100383053C CNB2004100536180A CN200410053618A CN100383053C CN 100383053 C CN100383053 C CN 100383053C CN B2004100536180 A CNB2004100536180 A CN B2004100536180A CN 200410053618 A CN200410053618 A CN 200410053618A CN 100383053 C CN100383053 C CN 100383053C
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- antimony pentachloride
- weisspiessglanz
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Abstract
The present invention particularly relates to a method for recovering and making antimony oxide from an antimony pentachloride solution, which comprises the following technical process: pretreatment, reduction, hydrolysis, desiccation and neutralization, wherein the pretreatment is composed of reduced pressure distillation of antimony pentachloride waste liquid, inorganic acid extraction and organic solvent extraction. The integrated technology of the present invention has the advantages of simple and easy operation, less raw material consumption, low cost and less investment. Compared with other recovery methods, the present invention has the advantages of low cost, no special production equipment, and easy technological condition control.
Description
Technical field
The present invention relates to the recovery method of a kind of metal and oxide compound thereof, relate in particular to and from antimony pentachloride solution, reclaim the method for producing weisspiessglanz.
Background technology
In fluorine refrigerant-12, fluorine refrigerant-22 etc. were produced, as catalysts, this catalyzer was mixed with the by product that produces in impurity and the reaction in can be because of raw material in use continuously and accumulates gradually and lost efficacy with antimony pentachloride.The composition that exists in the catalyzer that lost efficacy is quite complicated, and quinquevalence antimony, trivalent antimony and fluorine antimony chloride (SbCl are arranged
5-nFn, n=1 in the formula～5) and the higher hydrogen fluoride multiple organism different with boiling point of content, toxic is very big.As not handled and regenerating, all will cause very big harm to the environment and the mankind.
" Liaoning chemical industry " 1996 the 3rd interim " producing the research of stibium trioxide technological process from contain the antimony industrial residue " discloses the production process of producing stibium trioxide (weisspiessglanz) with dissolving with hydrochloric acid waste residue wet method, it with in the sodium hydroxide and spent catalyst after solid sediment be raw material, adopt the hydrochloric acid secondary to dissolve pre-treatment, reduction, hydrolysis, filter, pickling, neutralization, filter and drying process, its shortcoming is that sodium hydroxide and hydrochloric acid consumption are very big, cost height, hydrogen fluoride are not thorough in pre-treatment, and hydrofluoric existence has a strong impact on the processing of subsequent handling, especially thereby fluorion and antimony ion form complex compound and reduce percent hydrolysis, have reduced the rate of recovery of weisspiessglanz.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, the object of the present invention is to provide and a kind ofly can reduce raw material consumption, that can improve the rate of recovery simultaneously reclaims the method for producing weisspiessglanz from spent catalyst antimony pentachloride solution.
Technical scheme of the present invention: a kind of method produce weisspiessglanz that from antimony pentachloride solution, reclaims, this method comprise pre-treatment, reduction, hydrolysis, drying and in and technological process, this method pre-treatment is made up of following steps:
(1) underpressure distillation is carried out underpressure distillation to the antimony pentachloride waste liquid;
(2) mineral acid extraction is adopted the mineral acid extraction to the antimony pentachloride waste liquid after the underpressure distillation, gets inorganic phase solution after the extraction;
(3) organic solvent extraction adopts organic solvent extraction to above-mentioned inorganic phase solution, gets inorganic phase solution after the extraction.
To be controlled at 20 ℃～60 ℃, distillation time be 2 hours～5 hours to temperature during described underpressure distillation.
Mineral acid when mineral acid extracts is selected hydrochloric acid for use.
Organic solvent during organic solvent extraction is a kind of of benzene, toluene, tetracol phenixin or methylene dichloride or its mixture.
In the mineral acid extraction, as extraction agent, with 1mol/L～2mol/L salt acid elution organic phase, the volume ratio of organic phase and water was controlled at 1: 2～1: 4 with hydrochloric acid; Preferred 1: 3.2.
The basic solution used adopts sodium carbonate solution or ammoniacal liquor in this method and in the technological process.
In the N-process, with the yellow soda ash of 0.5mol/L～1.5mol/L, being neutralized to pH is 7～8, and temperature of reaction is controlled at 80 ℃～90 ℃.
Adopt dropping mode, preferred 85 ℃ of temperature of reaction when adding sodium carbonate solution.
Pre-treatment of the present invention comprises underpressure distillation, extraction, Cui Qu step again, reduced the consumption of sodium hydroxide, and removed the hydrogen fluoride that influences hydrolysis effect and etching apparatus, handle the waste gas that produces through this method and be easy to the alkali lye absorption, the waste water that produces in the technical process is easy to handle, reach pollution exhaust criteria, and do not have the waste residue generation in the technical process substantially, the weisspiessglanz rate of recovery can reach more than 90%, product content reaches more than 99%, integrated artistic is simple to operation, and raw material consumption is few, and cost drops into little.With respect to other recovery methods, cost of the present invention is low, the advantage that no special production equipment, processing condition are easy to control.
Description of drawings
Fig. 1 is for reclaiming the schematic flow sheet of producing weisspiessglanz from antimony pentachloride.
Embodiment
Below in conjunction with Figure of description, further specify the present invention with embodiment.
Embodiment 1: present embodiment reclaims weisspiessglanz from 250ml antimony pentachloride waste liquid, in conjunction with process frame chart shown in Figure 1, carries out as follows:
Step 1: get the antimony pentachloride waste liquid of 250ml, quinquevalence antimony, trivalent antimony and fluorine antimony chloride (SbCl are wherein arranged
5-nFn, n=1 in the formula～5) and the higher hydrogen fluoride multiple organism different of content, through underpressure distillation, temperature is controlled at 20 ℃～30 ℃ during distillation, till being distilled to no white smoke and emerging, steams thing and directly absorbs with alkali lye with boiling point.
Step 2: distillation finishes, and slowly joins in the hydrochloric acid of 2.0mol/L, and is to be cooled to room temperature, and the solution layering is left standstill after 1.0 hours with separating funnel and separated, and is the salt acid elution organic phase of 2.0mol/L with concentration.Organic phase and water ratio 1: 2.5 (volume ratio) just react completely it.
Step 3: after the dilute hydrochloric acid extraction, its solution also contains organic matters, further extracts with toluene again, and to guarantee the purity of product, the color of extraction liquid is till the shallow faint colour.
Step 4: antimony mainly exists with the pentavalent ionic species in the inorganic phase solution that iron powder reducing, hydrolysis extraction obtain, and with iron powder it is reduced into trivalent antimony, the SbCl that reduction obtains
3Hydrolysis, the English powder that generates white precipitates.
Step 5: N-process be drip while stirring concentration be the yellow soda ash of 1mol/L to English powder solution, 80 ℃ of neutral temperatures, when in and pH can stablize to 7～8 and be terminal point, suction filtration, drying obtain the antimonous oxide product, neutralization reaction:
Na
2CO
3+2SbOCl→Sb
2O
3+2NaCl+CO
2
Embodiment 2:
According to Fig. 1, as follows:
Change distillation temperature in the step 1 and be controlled between 35 ℃～45 ℃, all the other are identical with embodiment 1.Step 3 and step 4 are with embodiment 1.
Step 2: distillation finishes, and slowly joins in the dilute hydrochloric acid, and is to be cooled to room temperature, and the solution layering is left standstill after 1.0 hours with separating funnel and separated, and with the salt acid elution organic phase of concentration 2.0mol/L.The hydrochloric acid content deficiency is provided, and antimonic salt facile hydrolysis in the spent catalyst causes antimony and organic phase separation difficulty, and the dilute hydrochloric acid consumption is too much, and follow-up hydrolytic process wastewater flow rate is increased, so water intaking is 3.2: 1 (volume ratio) with the organic phase ratio.
Step 5: N-process be drip while stirring concentration be the yellow soda ash of 0.5mol/L to English powder solution, 85 ℃ of neutral temperatures, when in and pH can stablize to 7～8 and be terminal point, suction filtration, drying obtain the antimonous oxide product.
Embodiment 3:
According to Fig. 1, as follows:
Change distillation temperature in the step 1 and be controlled between 50 ℃～60 ℃, all the other are identical with embodiment 1.Step 3 and step 4 are with embodiment 1.
Step 2: distillation finishes, and slowly joins in the dilute hydrochloric acid, and is to be cooled to room temperature, and the solution layering is left standstill after 1.0 hours with separating funnel and separated, and with the salt acid elution organic phase of concentration 2.0mol/L.The hydrochloric acid content deficiency is provided, and antimonic salt facile hydrolysis in the spent catalyst causes antimony and organic phase separation difficulty, and the hydrochloric acid consumption is too much, and follow-up hydrolytic process wastewater flow rate is increased, so water intaking is 3.8: 1 (volume ratio) with the organic phase ratio.
Step 5: N-process be drip while stirring concentration be the yellow soda ash of 1.3mol/L to English powder solution, 90 ℃ of neutral temperatures, when in and pH can stablize to 7～8 and be terminal point, suction filtration, drying obtain the antimonous oxide product.
The test example: the various embodiments described above products obtained therefrom grade is as shown in table 1.
Table 1: product result
| Grade | Sb 2O 3％ | Impurity≤% | Whiteness % | Particle diameter (order) |
| Acceptable end product | ≥99.50 | 0.50 | ≥92 | ＞325 |
| Goods of inferior quality | ≥99.00 | 1.00 | ≥90 | ＞325 |
| Third grade product | ≥98.00 | 2.00 | ≥85 | ＞200 |
| Embodiment 1 | 99.52 | 0.50 | 88.0 | ＞325 |
| Embodiment 2 | 99.66 | 0.50 | 90.4 | ＞325 |
| Embodiment 3 | 99.58 | 0.46 | 89.5 | ＞325 |
As can be known, degree, foreign matter content and the particle diameter of the weisspiessglanz product weisspiessglanz that reclaims among the embodiment all reach the standard of acceptable end product from table, and almost the whiteness standard with goods of inferior quality is suitable on the whiteness.
Claims (9)
1. one kind is reclaimed the method produce weisspiessglanz from antimony pentachloride solution, this method comprise pre-treatment, reduction, hydrolysis, drying and in and technological process, it is characterized in that this method pre-treatment is made up of following steps:
(1) underpressure distillation is carried out underpressure distillation to the antimony pentachloride waste liquid;
(2) mineral acid extraction is adopted the mineral acid extraction to the antimony pentachloride waste liquid after the underpressure distillation, gets inorganic phase solution after the extraction;
(3) organic solvent extraction adopts organic solvent extraction to above-mentioned inorganic phase solution, gets inorganic phase solution after the extraction.
2. a kind of method produce weisspiessglanz that reclaims from antimony pentachloride solution according to claim 1, to be controlled at 20 ℃～60 ℃, distillation time be 2 hours～5 hours to temperature when it is characterized in that described underpressure distillation.
3. a kind of method of producing weisspiessglanz that reclaims from antimony pentachloride solution according to claim 1 is characterized in that the mineral acid when described mineral acid extracts is selected hydrochloric acid for use.
4. a kind of method of producing weisspiessglanz that from antimony pentachloride solution, reclaims according to claim 2, it is characterized in that in the described mineral acid extraction, as extraction agent, with 1mol/L～2mol/L salt acid elution organic phase, the volume ratio of organic phase and water was controlled at 1: 2～1: 4 with hydrochloric acid.
5. a kind of method of producing weisspiessglanz that reclaims from antimony pentachloride solution according to claim 4, the volume ratio ratio that it is characterized in that organic phase and water is 1: 3.2.
6. a kind of method produce weisspiessglanz that reclaims from antimony pentachloride solution according to claim 1, the organic solvent when it is characterized in that described organic solvent extraction is a kind of of benzene, toluene, tetracol phenixin or methylene dichloride or its mixture.
7. a kind of method produce weisspiessglanz that from antimony pentachloride solution, reclaims according to claim 1, in it is characterized in that and the basic solution of using in the technology adopt sodium carbonate solution or ammoniacal liquor.
8. a kind of method of producing weisspiessglanz that from antimony pentachloride solution, reclaims according to claim 7, when it is characterized in that neutralization procedure, with the yellow soda ash of 0.5mol/L～1.5mol/L, being neutralized to pH is 7～8, temperature of reaction is controlled at 80 ℃～90 ℃.
9. a kind of method of producing weisspiessglanz that from antimony pentachloride solution, reclaims according to claim 8, sodium carbonate solution adopts the dropping mode when it is characterized in that neutralization procedure, and temperature of reaction is 85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100536180A CN100383053C (en) | 2004-08-11 | 2004-08-11 | Method for recovering and making antimony oxide from antimony pentachloride solution |
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| CNB2004100536180A CN100383053C (en) | 2004-08-11 | 2004-08-11 | Method for recovering and making antimony oxide from antimony pentachloride solution |
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| CN100383053C true CN100383053C (en) | 2008-04-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820645A (en) * | 2014-03-21 | 2014-05-28 | 山东腾跃化学危险废物研究处理有限公司 | Antimony pentachloride waste liquid treatment system |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408163B (en) * | 2013-08-28 | 2014-11-26 | 山东东岳化工有限公司 | Treatment method of waste liquid in production of organic fluoride |
| CN108458344B (en) * | 2018-06-28 | 2023-09-26 | 中化蓝天霍尼韦尔新材料有限公司 | Pretreatment equipment and treatment method of antimony pentachloride waste catalyst |
| CN109534396A (en) * | 2018-12-26 | 2019-03-29 | 浙江工业大学 | A kind of transition state sb oxide and preparation method thereof |
| CN110902719A (en) * | 2019-10-11 | 2020-03-24 | 江苏梅兰化工有限公司 | Method for recovering antimony trioxide from difluorochloromethane reaction residual liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1495032A (en) * | 1974-08-17 | 1977-12-14 | Kali Chemie Ag | Process for the recovery of antimony pentachloride from spent catalyst solutions |
| CN1040358A (en) * | 1988-08-01 | 1990-03-14 | 纳幕尔杜邦公司 | By being separated and the hydrofluoric method of fractionation by distillation |
-
2004
- 2004-08-11 CN CNB2004100536180A patent/CN100383053C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1495032A (en) * | 1974-08-17 | 1977-12-14 | Kali Chemie Ag | Process for the recovery of antimony pentachloride from spent catalyst solutions |
| CN1040358A (en) * | 1988-08-01 | 1990-03-14 | 纳幕尔杜邦公司 | By being separated and the hydrofluoric method of fractionation by distillation |
Non-Patent Citations (2)
| Title |
|---|
| 从含锑工业废渣中制取锑白工艺过程的研究. 李景国，姜胤.辽宁化工，第3期. 1996 * |
| 锑白生产新工艺-用三氯化锑水解法制取三氧化二锑. 郑文裕，刘希澄，沈展中，赖远雄.湿法冶金，第3期. 1991 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820645A (en) * | 2014-03-21 | 2014-05-28 | 山东腾跃化学危险废物研究处理有限公司 | Antimony pentachloride waste liquid treatment system |
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